Weakened Hydrogen‐Bond Molecular Crowding Electrolyte Enabling (002)‐Textured Zinc Deposition for Dendrite‐Free Zinc Ion Batteries

The irreversibility and dendritic growth of zinc (Zn) metal during charge/discharge cycling lead to poor Coulombic efficiency (CE) and short cycle life of aqueous zinc‐ion batteries (AZIBs). Here, a weakened hydrogen‐bond molecular crowding electrolyte (MCE) is developed using polyvinyl pyrrolidone (PVP‐I) as a dynamic chelation‐crowded ligand. Leveraging its strong electronegativity and hydrogen‐bonding capability, PVP‐I weakens the hydrogen‐bonding networks of water, thereby orchestrating the solvation structure and deposition kinetics. This synergy not only suppresses hydrogen evolution and promotes (002)‐textured zinc deposition but also replenishes the cathode capacity. Consequently, the highly reversible Zn anode delivers a stable cycling life of 3000 cycles with an average CE of 99.86% at 10 mA cm −2 . Zn||Zn symmetric cells achieve ultra‐long lifespan exceeding 8 000 h, excellent rate performance up to 25 mA cm −2 , and robust temperature endurance at 50°C. Furthermore, the proposed MCEs enable stable operation of Zn‐I 2 full battery for over 7000 cycles at room temperature and 3200 cycles at 50°C. This work underscores the promise of macromolecular complex additives in redefining MCE design toward highly durable AZIBs.